Leubner Sebastian, Stäglich Robert, Franke Julia, Jacobsen Jannick, Gosch Jonas, Siegel Renée, Reinsch Helge, Maurin Guillaume, Senker Jürgen, Yot Pascal G, Stock Norbert
Department for Inorganic Chemistry, University of Kiel, Max-Eyth Strasse 2, 24118, Kiel, Germany.
Inorganic Chemistry III, University of Bayreuth, Universitätsstrasse 30, 95447, Bayreuth, Germany.
Chemistry. 2020 Mar 23;26(17):3877-3883. doi: 10.1002/chem.201905376. Epub 2020 Mar 9.
Herein is reported the utilization of acetonitrile as a new solvent for the synthesis of the three significantly different benchmark metal-organic frameworks (MOFs) CAU-10, Ce-UiO-66, and Al-MIL-53 of idealized composition [Al(OH)(ISO)], [Ce O (OH) (BDC) ], and [Al(OH)(BDC)], respectively (ISO : isophthalate, BDC : terephthalate). Its use allowed the synthesis of Ce-UiO-66 on a gram scale. While CAU-10 and Ce-UiO-66 exhibit properties similar to those reported elsewhere for these two materials, the obtained Al-MIL-53 shows no structural flexibility upon adsorption of hydrophilic or hydrophobic guest molecules such as water and xenon and is stabilized in its large-pore form over a broad temperature range (130-450 K). The stabilization of the large-pore form of Al-MIL-53 was attributed to a high percentage of noncoordinating -COOH groups as determined by solid-state NMR spectroscopy. The defective material shows an unusually high water uptake of 310 mg g within the range of 0.45 to 0.65 p/p°. In spite of showing no breathing effect upon water adsorption it exhibits distinct mechanical properties. Thus, mercury intrusion porosimetry studies revealed that the solid can be reversibly forced to breathe by applying moderate pressures (≈60 MPa).
本文报道了乙腈作为一种新型溶剂用于合成三种结构显著不同的基准金属有机框架材料（MOF），即CAU-10、Ce-UiO-66和Al-MIL-53，其理想组成分别为[Al(OH)(间苯二甲酸酯)]、[CeO(OH)(对苯二甲酸酯)]和[Al(OH)(对苯二甲酸酯)]（间苯二甲酸酯：间苯二甲酸，对苯二甲酸酯：对苯二甲酸）。使用该溶剂能够以克级规模合成Ce-UiO-66。虽然CAU-10和Ce-UiO-66表现出与其他地方报道的这两种材料相似的性质，但所得到的Al-MIL-53在吸附亲水性或疏水性客体分子（如水和氙）时没有结构灵活性，并且在较宽的温度范围（130 - 450 K）内以大孔形式稳定存在。Al-MIL-53大孔形式的稳定归因于通过固态核磁共振光谱测定的高比例非配位-COOH基团。这种有缺陷的材料在0.45至0.65 p/p°范围内表现出异常高的吸水量，为310 mg g。尽管在吸水时没有呼吸效应，但它表现出独特的力学性能。因此，压汞孔隙率法研究表明，通过施加适度压力（≈60 MPa），该固体可以被可逆地迫使产生呼吸效应。
